Inorganic-organic hybrid semiconductor nanofibers of CdS/CHA (CHA = cyclohexylamine) were successfully synthesized by a simple solvothermal method. The fibers obtained had average diameter of 20 nm and length of several micrometers. In these fibers, periodic layer-like sub-nanometer structures with thickness of approximately 3 nm were identified by high-resolution transmission electron microscope (HR-TEM). The absorption of the hybrids exhibited a large blue-shift in contrast to the bulk, which was attributed to strong quantum confinement effect (QCE) induced by internal sub-nanometer structures. Pure hexagonal wurtzite CdS (H-CdS) nanorods were also obtained by extracting the CdS/CHA hybrids with dimethyl formamide (DMF). The rods obtained had average diameter of 20 nm and length of 200 nm. A CdS/CHA/polyvinyl alcohol (PVA) composite film emitting white light was prepared by spin coating.